X-ray photoelectron spectroscopy (XPS) and cathodoluminescence (CL) method have been employed to study the chemical composition and the oxygen vacancy concentration of HfO2, Sc2 O3 and (HfO2)1−x(Sc2O3)x films. It was found that the increase of Sc content led to monotonic decreasing the Hf4f7/2 and Sc2p3/2 binding energies indicating to form solid solution (HfO2)1−x(Sc2O3)x. All the samples characterized by the intensive CL spectra with maximum around 3 eV which originated due to some radiative recombination emission caused by oxygen deficiency. The concentration of oxygen vacancy in the Sc-doped HfO2 is sensitive to the Sc content and as a result the intensity of CL spectra of (HfO2)1−x(Sc2O3)x is lower that those of pure HfO2 and Sc2O3.